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Calculation of infrared spectra for adsorbed molecules from the dipole autocorrelation function

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Abstract

Accurate ab initio investigations of vibrational properties for adsorbed molecules typically involve massive computational resources. We show that by using the autocorrelation function of the dipolar momentum to compute the infrared spectrum of the porphyrin and Co-porphyrin adsorbed on silver surface we can offer reliable data with a moderate computational effort. We test our implementation by comparing the results with benchmark and with experiment data. As our focus is to address adsorbed molecules, we exhaustively investigate the effect of the surface upon the IR spectrum as well as the influence of van der Waals interactions on the final IR spectra. The connection between molecule-surface charge transfer and the IR signature of adsorbate is also discussed.

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The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

The work was founded by the UEFISCDI, project PN-III-P4-ID-PCE-2020-0824.

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  1. National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, 400293, Cluj-Napoca, Romania

    Luiza Buimaga-Iarinca & Cristian Morari

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  1. Luiza Buimaga-Iarinca
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CM designed and coordinated the study. LBI was involved into paper writing and data analysis.

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Correspondence to Cristian Morari.

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Buimaga-Iarinca, L., Morari, C. Calculation of infrared spectra for adsorbed molecules from the dipole autocorrelation function. Theor Chem Acc 141, 69 (2022). https://doi.org/10.1007/s00214-022-02932-3

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